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International Scholarly Research Network

ISRN Renewable Energy

Volume 2012, Article ID 142857, 13 pages

Review Article
Tin-Catalyzed Esterification and Transesterification
Reactions: A Review

Arthur Batista Ferreira, Abiney Lemos Cardoso, and Marcio Jose da Silva
Chemistry Department, Federal University of Vicosa, 36570-000 Vicosa, MG, Brazil

Correspondence should be addressed to Marcio Jose da Silva, silvamj2003@ufv.br

Received 17 April 2012; Accepted 5 September 2012

Academic Editors: B. Chen, K. T. Lee, and Y.-C. Lin

Copyright 2012 Arthur Batista Ferreira et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly

The recent increase in the world biofuels demand, along with the need to reduce costs while improving the environmental
sustainability of the biodiesel production, have led to the search for catalysts that should be economically viable, ecient, and
environmentally friendly. This paper reviews recent research and development of organic and inorganic tin catalysts; focusing
on kinetic properties and catalytic activity in two key reactions for biodiesel production: free fatty acids (FFA) esterification
and triglycerides (TG) transesterification. First the basic knowledge of homogeneous tin catalysts in esterification reactions of
dierent carboxylic acids is provided. Second, main advances obtained in the study of FFA esterification reactions catalyzed by
tin chloride are covered. The eect of the principal parameters of reaction on the yield and rate of alkyl esters production is
described. Kinetic measurements allowed the determination of the activation energy (46.79 kJ mol1 ) and a first-order dependence
in relation to both FFA and tin chloride catalyst concentration. Aspects related to recycling of the tin chloride catalyst in phase
homogeneous are discussed. Third the advances obtained in the development of homogeneous catalysts based on tin complexes in
transesterification reactions are summarized. Finally, results obtained from the use of tin organometallics compounds in reactions
of vegetable oils transesterification reactions are concisely presented. The optimization of processes catalytic homogeneous utilized
in the transesterification reactions can contribute to the improvement of the technology biodiesel production.

1. Introduction a large amount of euents and residues are generated during

the products neutralization. In addition, homogeneous
The demand for renewable energy sources has made biofuels alkaline catalysts are corrosive and are nonrecyclable, that
an attractive alternative that can reduce the consumption of comprises the main disadvantags of its use in the biodiesel
the traditional fossil fuels [1]. Biofuels have a closed loop for production.
the CO2 , that is, the main greenhouse gas and besides that Nowadays, most of the biodiesel consumed is produced
they can contribute to the reduction in the emissions of toxic by transesterification of edible vegetable oils, which are
gases such as SO2 , SO3 , and CO [2]. Among the biofuels responsible for 65% of the final prices [5]. Alternative-
currently explored, biodiesel deserves highlights because it feedstoks have been proposed for their production, such as
can be used pure or in blends with the diesel fuel. Biodiesel animal fats, waste frying, and vegetable oil refining processes
is a renewable fuel, biodegradable, and less polluting than rejects. Nevertheless, these low-cost raw materials contain
diesel, obtained from the triglycerides transesterification high FFA amount and are not compatible with alkaline
(Figure 1) or esterification of free fatty acids (FFA) with short catalysts, resulting thus in the formation of soaps, which
chain alcohol (methyl or ethyl alcohol) (Figure 2) [3]. hampered the separation of the esters and glycerol, and
Biodiesel has been considered as a green fuel, however, consequently reduces biodiesel yields.
its production processes results in a high environmental The production of biodiesel from raw materials with
impact, because it is based on homogeneous alkaline catalysts high content of FFA requires the use of homogeneous acid
(i.e., KOH, NaOH, or NaOCH3 ), which although inexpen- catalysts [6]. Usually, a two-stage process is performed,
sive, provoke serious environmental drawbacks [4]. Firstly, where the first step (i.e., FFA esterification) is acid-catalyzed
2 ISRN Renewable Energy



Figure 1: Transesterification reaction of triglycerides (TG) for biodiesel production.

(CH2 )n ROH (CH2 )n
+ H2 O
n = 1012 Acidic catalyst n = 1012

Figure 2: Esterification reaction of fatty acids for biodiesel production.

and the second step (i.e., triglycerides transesterification) Table 1: SnCl2 -catalyzed esterification of benzoic acid with propyl
is base-catalyzed; normally, both processes occur under alcohola [7].
mild reaction conditions (60 C). An option is converting
Run SnCl2 (mmol) Time (h) Yield (%)b
both FFA and TG into biodiesel in a one-stage process.
1 1 20 94
However, these processes require higher temperatures (up to
130 C) and stronger mineral acids such as H2 SO4 as catalyst. 2c 1 20 13
Actually, the use of homogeneous Brnsted acid catalysts has 3 0.1 20 51
also similar problems to those of the alkaline catalysts: large 4 0.2 40 80
euents generation and salts from the neutralization steps, 5d 1 20 25
high reactor corrosion, and non-reuse of the catalysts. a
All reactions were carried out with benzoic acid (2 mmol) and propyl alco-
Thus, overcome the technological challenges related to hol (2 mL) at 100 C temperature, unless otherwise stated. b Isolated yield
the catalytic processes can increase the scope of raw materials based on 1. c Propyl alcohol (2 mmols) in dioxane (2 mL). d Temperature
60 C.
applicable in the biodiesel production and simultaneously
reduce environmental impact of their productive processes
[16, 17]. or catalyst load, as well as the reaction temperature, increases
the ester yield (Scheme 1).
Indeed, the best yield was reached performing reaction
2. Tin Catalysts by 20 hours at 100 C temperature and using 10 mol%
Lewis acids are an important class of acid catalysts. They SnCl2 in relation to benzoic acid (Run 1, Table 1). The
are milder than Brnsted acids, but their utilization has secondary alcohol (isopropyl alcohol, Run 2, Table 1) was
been significantly increased. Lewis acids are species with less reactive. The authors also assessed the eect of the
deficiency of electrons that can act activating substrates rich carboxylic acid nature on the esters yield obtained in SnCl2 -
in electrons. Frequently, Lewis acid-base adducts are the catalyzed esterification with propyl alcohol and main results
key intermediates in the acid-catalyzed reactions. However, are displayed in Table 2.
although Lewis acid catalysts are widely used in organic In general, Cho and co-workers observed that high yields
synthesis, The most of them are dicult to handle and were obtained in the esterification reactions of aromatic,
unstable in presence of air or water, such as SnCl4 , AlCl3 , and unsaturated and saturated carboxylic acids with propyl
BF3 , which yet hamper their use in greater scale. alcohol. They suggested that despite the conjugation of
the carbonylic double bond with the double bonds of the
aromatic ring, the carbonyl reactivity was not significantly
2.1. Tin Chloride Catalyzed-Esterification Reactions. Tin (II) aected. Consequently, good yield up to 80% was reached,
catalysts are widely used at industrial scale in polymerization except when isopropyl alcohol was used (second entry,
of L-lactide, as well as polyesters synthesis. On the other Table 2).
hand, the use of organotin alkoxy is widely described in
transesterification reactions [7, 18]. Comparatively to other 2.1.1. Tin Chloride Catalyzed-FFA Esterification Reactions.
Lewis acids, SnCl2 has attractive properties such as being Stable Lewis acids, water tolerant and easy to handle as
a stable solid, highly tolerant to water, easily handled, and the SnCl2 , are potentially attractive for the production of
less corrosive. In a pioneering study, Cho and coworkers biodiesel. Moreover, a recent work showed that although
[7] described the use of SnCl2 H2 O as catalyst in carboxylic used in homogeneous phase, the SnCl2 catalyst can be easily
acid esterification reactions with dierent alcohols under recovered and reused in glycerol esterification reactions [18].
stoichiometric proportions. Initially, those authors focused Thus, the use of Lewis acid catalysts in preesterification steps
their attention on the benzoic acid esterification with propyl of waste cooking oils, fats, and lipidic feedstock, which can be
alcohol (Table 1). They found that increasing reaction time converted into biodiesel, should be highly useful. Actually,
ISRN Renewable Energy 3

O H3 C O O
M O +

Scheme 1

Table 2: SnCl2 -catalyzed esterification of carboxylic acids with of alcohol excess on conversion of oleic acid into ester, free-
propyl alcohol [7]a . catalyst reactions were performed and results are shown in
Figure 3 [8].
Carboxylic acid Yield (%)b
Despite of high molar ratio of ethyl alcohol : oleic acid
COOH 94 (120 : 1), the reaction without catalyst reached only a poor
67c conversion (ca. 10%) after 12 hours monitoring the reaction.
80d Contrarily, using a Lewis acid catalyst (SnCl2 2H2 O), a
conversion of 87% was achieved at the same reaction time.
Probably the catalyst Sn (II) activates the carbonyl group of
O COOH the fatty acid, favoring his attack by the hydroxyl group of
ethanol, thereby generating an increased formation of ethyl
99 The carbon chain length of alcohol can aect both the
HO COOH rate and also the conversion of fatty acid in esterification
reactions (Figure 4) [8].
A dierent behavior was observed in terms of alcohols
95 reactivity in reactions catalyzed by SnCl2 . In general, after
1 hour reaction, methyl and ethyl alcohol reacted at the
same rate, and the same can be stated about propyl and
91 butyl alcohol, although this last pair has reacted more slowly.
However, at longer reaction times, the reactivity of two first
alcohols undergoes a higher split. After 12 hours reaction,
COOH the conversion reached in esterification of both methyl and
Reaction conditions: SnCl2 (1 mmol), carboxylic acid (2 mmol), propyl ethyl alcohol became three times higher than propyl and
alcohol (2 mL), 100 C temperature, and 20 hours reaction. butyl alcohol. As general tendency, da Silva and coworkers
b Isolated yield.
concluded that in the SnCl2 -catalyzed oleic acid esterification
c Isopropyl alcohol was used.
d SnCl 0.2 mmol and 40 hours reaction.
an increase on carbon chain length of alcohol resulted in
a decrease in conversion. This result is in agreement with
the nucleophilicity of the alcohols, which decreases with the
increase of their carbon chain.
On the other hand, the carbon chain length and double
the presence of FFA in the raw material causes serious bonds number of the fatty acid can also aect both selectivity
processing problems in standard biodiesel manufacturing, and conversion of esterification reactions. This eect was
since they are readily saponified by the homogeneous alkali assessed and the results are displayed in Table 3 [8].
catalyst used to transesterify the TG, leading to a loss of A variation of the size of the fatty acid carbon chain
catalyst as well as increased products, purification costs [19]. (in range C14 C18 ), did not significantly influence the
The main approach to improve the processing of oils conversion and the reaction selectivity after 12 hours run [8].
which contain FFAs in large amount is firstly to promote a A similar result was found studying this eect in Brnsted
step of acid-catalyzed esterification before transesterification. acid-catalyzed FFA esterification (i.e., H3 PW12 O40 catalyst)
If the FFA amount in feedstock is lowered to no more [20]. It is ended then that the tin chloride eciently catalyzed
than 0.5 wt%, it can then be processed under standard the saturated and unsaturated FFA esterification with ethyl
transesterification reaction conditions (i.e., homogeneous alcohol.
alkaline catalysis conditions). The performance of the SnCl2 2H2 O (Lewis acid) and
Inspired by these findings, Cardoso and coworkers [8] H2 SO4 (Brnsted acid) were compared and the results are
have investigated the catalytic activity of the SnCl2 2H2 O in presented in Table 4 [9].
FFA esterification reactions to produce biodiesel. However, The two acid catalysts, in spite of bearing so dierent
dierently than described by Cho and coworkers [7], da features and structures, displayed much similar activities as
Silva and coworkers use a large excess of alcohol in all the can be confirmed by the attainment of comparable oleic
SnCl2 2H2 O-catalyzed reactions. This was probably the first acid conversion into ethyl oleate in Table 4. A kinetic study
work that assessed the use of the SnCl2 as catalyst in the performed by Cardoso and coworkers [9] suggested a first-
biodiesel production process. Aims to investigate the eect order dependence of reaction rate in relation to acid oleic
4 ISRN Renewable Energy

100 Table 3: Esters yield and selectivity obtained from SnCl2 -catyalyzed
esterification with ethyl alcohola [8].

80 Ethyl ester
Exp. Fatty acid CN/DBb conversion
(%)c (%)c
Conversion (%)

1 Myristic 14 : 0 90 97
2 Palmitic 16 : 0 86 95
40 3 Stearic 18 : 0 87 97
4 Oleic 18 : 1 90 95
20 5 Linoleic 18 : 2 92 93
Reaction conditions: ethyl alcohol (120 mmol), fatty acid (1 mmol),
SnCl2 2H2 O (0.1 mmol), reflux temperature, and reaction time 12 h.
0 b CN and DB refer to the number of carbons and double bonds in the
0 100 200 300 400 500 600 700 800 carbonic chain of the FFA, respectively.
c Calculated from the areas of the ethyl esters GC peaks.
Time (min)

Reaction catalyzed by SnCl2 2H2 O

Reaction without catalyst Table 4: Conversion and selectivity of the oleic acid esterification
with ethyl alcohol catalyzed by SnCl2 2H2 O or H2 SOa4 [9].
Figure 3: Trends of oleic acid conversion into ethyl oleate in
presence or absence of SnCl2 catalyst [8]. Reaction conditions: SnCl2 2H2 O H2 SO4
Time (h)
ethyl alcohol (120.0 mmol), oleic acid (1.0 mmol), SnCl2 2H2 O. Conversion Selectivity Conversion Selectivity
(0.10 mmol), temperature (75 C), and oleic acid conversion was (%) (%) (%) (%)
determined by titration against KOH solution (0.010 molL1 ).
0 0 0 0 0
1 62 92 65 90
100 2 93 94 92 89
90 4 90 95 94 87
80 6 90 93 95 89
70 8 91 93 94 88
Conversion (%)

60 Reactions conditions: ethyl alcohol (120.0 mmol), oleic acid (1.0),
SnCl2 2H2 O (0.40 mmol), H2 SO4 (0.10 mmol), temperature (75 C), and
50 oleic acid conversion was determined by GC analyses and titration against
40 KOH (0.010 molL1 ).
20 oleic acid with ethyl alcohol. The approach employed was
10 similar to that made by Berrios and coworkers [21], but
0 with small modifications, which was based on the following
0 100 200 300 400 500 600 700 800
Time (min) (i) The esterification reaction was a reversible homoge-
Methyl alcohol n-propyl alcohol neous process, the operating conditions used were
Ethyl alcohol n-butyl alcohol controlled aiming that the reaction rate was limited
only by the chemical reaction rate (no diusion
Figure 4: Eect carbon chain length of alcohol on reaction rate
of SnCl2 -catalyzed oleic acid esterification [8]. Reaction condi-
tions: alcohol (670.0 mmol), oleic acid (3.5 mmol), SnCl2 2H2 O (ii) The rate of the noncatalyzed reaction was negligible
(0.35 mmol), temperature (75 C), 12 hours reaction, and kinetic relative to the catalyzed reaction.
data obtained from titration against KOH solution (0.01 molL1 ).
(iii) The excess of ethyl alcohol employed was high
enough for its concentration to remain constant
throughout the process.
concentration in both reactions. They determined the order
in relation to SnCl2 concentration carrying out reactions From of the resulting data shown in Table 5, the curve of
with dierent concentrations of the catalyst and a 0.87 value the Figure 6 was constructed. Employing a linear regression
was found. The influence of reaction temperature was also method, the angular coecient (-E/R) of the curve obtained
assessed and the results are shown in Figure 5. allows us to calculate the activation energy of this process,
Herein, as can be seen, an increase in the reaction temper- which was equal to 46.79 kJ.mol1 .
ature causes a significant increase in the final conversion as This value obtained was very close to those values of
well as in the reaction initial rate. Those authors performed activation energy obtained by Berrios and coworkers [21];
a kinetic study of SnCl2 -catalyzed esterification reaction of those authors determined that the activation energy of this
ISRN Renewable Energy 5

100 10.5
80 11
Conversion (%)

60 11.5

40 12
20 12.5
0 100 200 300 400 500 600 700 800 2.85 2.90 2.95 3 3.05 3.1 3.15 3.2 3.25 3.3
Time (min) 1/T (K 1 )

25 C 55 C Figure 6: Linear plot of ln k versus 1/T resulting from tin chloride-

35 C 65 C catalyzed esterification of oleic acid with ethyl alcohol [9].
45 C 75 C

Figure 5: Eect of the temperature on the SnCl2 -catalyzed Table 6: SnCl2 -catalyzed esterification of oleic acid with ethyl
esterification reaction of oleic acid with ethyl alcohol [9]. Reaction alcohol: catalyst recovery yields and substrate conversiona [10].
conditions: alcohol ethyl (670.0 mmol), oleic acid (3.5 mmol),
SnCl2 2H2 O (0.35 mmol), 12 hours reaction, and kinetic data Run Recovery yields (%) Oleic acid conversion (%)b
obtained from titration against KOH solution (0.01 molL1 ). 1 90 92
2 87 87
Table 5: Values of rate constant (k) and linear correlation 3 90 92
coecient (R2 ) for the SnCl2 -catalyzed oleic acid esterification with 4 91 91
ethyl alcohol [9]. 5 90 91
ln[oleic acid]/ln [oleic acid]0 = kt 6 89 89
Temperature (K) R2 a
k values (s1 ) Reaction conditions: ethyl alcohol (120.0 mmol), Oleic acid (10.0 mmol),
SnCl2 2H2 O (0.1 mmol), 12 hours, and reflux temperature.
308 3.08 106 t 0.91 b Calculated from the GC peaks areas of the ethyl oleate.
318 4.29 106 t 0.95
328 9.74 106 t 0.98
338 16.52 106 t 0.99 found that the level of tin in the biodiesel produced was lower
348 21.53 106 t 0.97 than 1 ppm [10].
The SnCl2 -catalyzed FFA esterification present in the
waste cooking oil samples was recently investigated and
same reaction catalyzed by H2 SO4 was equal to 50.74 kJ a comparison between its activity and that of a sulfonic
mol1 and 42.76 kJ mol1 . catalyst (p-toluenesulfonic acid, pTSA) was also performed
The recovery and reusability of SnCl2 2H2 O catalyst (Figure 7) [22].
under homogeneous reaction conditions was investigated in In the reaction conditions studied, pTSA and SnCl2
FFA esterification to produce biodiesel [10]. In this work, catalysts displayed a very similar behavior, however, a direct
Cardoso and coworkers [10] dedicated special attention to comparison of theirs activity is hard because dierent
determine the tin content in the samples of biodiesel pro- mechanism may be involved as consequence of the dierent
duced. Results described in Table 6 show that SnCl2 2H2 O acidity of two catalysts.
catalyst, though used in homogeneous phase, can be e- The activity of both Lewis or Brnsted acid catalysts
ciently recovered from the reaction medium. The recycle in esterification reactions may be drastically aected by the
process consisted in the ethyl alcohol evaporation, filtration water generated as by-product of reaction or present since
of the solid remaining, and washing the hexane. After dried, its initial period, especially when are used low cost raw
the tin catalyst was weighted and reused again in another materials which are rich in FFA. Literature has reported some
catalytic runs (Table 6). important results about the eect of the water concentration
The residual tin concentration in the biodiesel samples in Brnsted acid-catalyzed esterification reactions. Recently,
was determined by AAS analyses. The biodiesel samples were Park and coworkers investigated the water eect esterifica-
analyzed by the standard method of addition due to the low tion with methyl alcohol of the pure oleic acid and added
levels of tin expected. High linear correlation coecients soybean oil in presence of sulfuric acid as homogeneous
(R2 ) were obtained showing that the methodology for catalyst [22]. It was found that the inhibiting eect of
quantification of tin in the biodiesel was ecient. It was water was more dominant under Amberlyst-15 (another
6 ISRN Renewable Energy

100 100
90 90
80 80
70 70

Conversion (%)
Conversion (%)

60 60
50 50
40 40
0 20 40 60 80 100 120 140 160 180 200 220 240 0
0 30 60 90 120 150 180 210 240
Time (min)
Time (min)
Water 0% wt Water 2% wt
SnCl2 2H2 O
Water 0.1% wt Water 5% wt
Water 1% wt
Figure 7: Acid-catalyzed FFA esterification with ethyl alco-
hol in WCO samples [10]. Reaction conditions: ethyl alcohol Figure 8: Eect of water on the SnCl2 -catalyzed esterification of the
(380.0 mmol, 21.8 mL), WCO (13.0 g; 13.2 mL), SnCl2 2H2 O FFA presents in the WCO samples with ethyl alcohola [23]. Reaction
(0.30 mmol), pTSA (1.20 mmol), reflux temperature. conditions: ethyl alcohol (380.0 mmol, 21.8 mL), waste cooking oil
(13.0 g, 13.2 mL), SnCl2 2H2 O (0.30 mmol), water initially added
(0.05.0% wt.), reflux temperature.

catalyst investigate) than under sulfuric acid due to the

poisoning of acid sites on Amberlyst-15 by water. When
sulfuric acid was used as a catalyst, a molar ratio of 1 : 6 refined oil or more pure feedstock is used as raw material it
of oil to methanol eliminated the hindrance of water until is responsible by approximately 80% of the biodiesels final
a 5% addition of water. Cardoso and co-workers assessed cost. For these reasons, acid catalysts that are capable of
this eect in H3 PW12 O40 -catalyzed oleic acid esterification eectively processing less costly feedstock high in FFAs and
reactions [20]. They found that although high Brnsted water content with a simpler less costly processing method
acidity of H3 PW12 O40 catalyst, an addition of 5% wt water acquire a strategic position.
to the reaction resulted in a reduction on esters yield of the In general, acid-catalyzed transesterification reactions
90% for 40% after 8 hours reaction [9]. On the other hand, are performed at high alcohol-to-oil molar ratios, high
in general Lewis acid catalysts are few tolerant to water; in temperatures and pressures, and high catalyst concentration.
addition, there is few works about this aspect in the literature. Acid-catalyzed reactions require the use of high alcohol: oil
However, investigating the same eect in SnCl2 -catalyzed molar ratio in order to obtain good esters yields within
waste cooking soybean oil esterification reactions, da Silva reasonable reaction time. Among the most common acid
and coworkers [23] verified that tin chloride was much more catalysts employed the vegetal oil transesterification reac-
water tolerant than H3 PW12 O40 catalyst (Figure 8). tions highlights the sulfuric acid. Freedman and coworkers
As a conclusion, the tin chloride catalyst is a water showed that the methanolysis and ethanolysis reactions of
tolerant Lewis acid, highly active in FFA esterification, less soybean oil, both catalyzed by sulfuric acid (ca. 1 mol%)
corrosive and easily handled. All these features comprise the with an alcohol/oil molar ratio of 30 : 1 at reflux temperature
positive aspects of their use in FFA esterification reactions for (ca. 65 C or e 78 C resp.,) takes 50 h and 18 hours to
biodiesel production from the inexpensive lipidic feedstock. reach complete conversion of the vegetable oil (>99%) [25].
Indeed, both reaction temperature and catalyst load are key
aspects in TG acid-catalyzed transesterification. Canakci and
2.2. Tin Catalyzed-Transesterification Reactions Van Gerpen used dierent amounts of sulfuric acid (1, 3, and
5 wt %) in the transesterification of grease with methanol
2.2.1. Brnsted Acid-Catalyzed Transterification Reactions:
[26]. In these studies, a rate enhancement was observed with
A brief Introduction. Homogeneous alkaline catalysts are
the increased amounts of catalyst, and ester yield went from
known to be more active than counterpart homogeneous
72.7 to 95.0% as the catalyst load was increased from 1 to
acid catalysts. Indeed, the homogeneous acid-catalyzed
5 wt%.
transesterification reaction is about 4000 times slower than
the homogeneous base-catalyzed reaction [24]. However,
when the reactions are performed under alkaline catalysis 2.2.2. Catalysts Based on Coordination Complexes of Tin(II)-
conditions, the FFA content and water of the oil feed- Pyrone Applied on TG Transesterification Reactions. A signif-
stock should be rigorously controlled. Consequently, when icant advance on use of tin complexes in transesterification
ISRN Renewable Energy 7


+ NaOH O
2 + MCl2 O O

Figure 9: Synthesis of metal-pyrone complexes (M = Sn, Pb, Hg, or Zn) [11].

reactions was achieved by Abreu and coworkers [11, 27, Table 7: Main results obtained from soybean oil transesterification
28]. Those authors described the use of coordination com- with methyl alcohol catalyzed by NaOH, H2 SO4 or [Sn(II)(3-
pounds with pyrone ligand (3-hydroxy-2-methyl-4-pyrone) hydroxy-2-methyl-4-pyrone)2 (H2 O)2 ], complex, I catalysta, b [11].
and divalent metal cations (M = Sn(II), Pb(II), Zn(II), and
Entry Catalystc Time (h) Yield (%)c
Hg(II), as catalysts in oil vegetable transesterification with
1 NaOH 1 0.173
methyl alcohol. These complexes can be obtained from the
reaction of the pyrone ligand with metal halide in presence 2 NaOH 3 5.135
of NaOH (Figure 9), as was described firstly by Abreu and 3 NaOH 6 6.912
coworkers [11, 27, 28]. 4 NaOH 10 9.904
The activity of metal complexes catalysts was compared 5 H2 SO4 1 1.364
with the activity of others homogeneous catalysts tradition- 6 H2 SO4 3 2.201
ally used in transesterification reactions (NaOH and H2 SO4 ). 7 H2 SO4 6 4.700
Herein, because tin complexes catalysts were much more 8 H2 SO4 10 6.992
active than other metal complexes catalysts, only their results 9 Sn(II)-pyrone 1 37.139
are displayed in Table 7 [11]. 10 Sn(II)-pyrone 3 91.116
The results obtained by Ziani and coworkers showed that
11 Sn(II)-pyrone 6 93.180
the [Sn(II)(3-hydroxy-2-methyl-4-pyrone)] complex was the
most active catalyst in transesterification reaction studied, 12 Sn(II)-pyrone 10 22.125
reaching conversions higher than those obtained by alkaline Reaction conditions: molar proportions of methanol : oil : catalyst
(400 : 100 : 1) were fixed for all experiments, temperature (80 C), stirring
catalyst (NaOH) [11]. However, for longer reaction times magnetic (1000 rpm).
(ca. 10 hours), occurred a significant decrease on reaction b [Sn(II)(3-hydroxy-2-methyl-4-pyrone) (H O) ], I catalyst.
2 2 2
conversion; this fact suggests that the process should be c Percent of mass of recovered ester per initial mass of soybean oil.

interrupted after 5-6 hours reaction.

Abreu and coworkers investigated the activity of the
tin(II)-pyrone complex in transesterification reactions of
biodiesel manufacturing is restricted mainly because they are
soybean vegetable oil with dierent alcohols and found that
active only in transesterification with methyl alcohol, which
tin(II)-pyrone complex was more active than sulfuric acid
is normally obtained from the nonrenewable sources.
in all catalytic runs [11]. Moreover, they assessed these two
The use of Lewis acid metals as catalysts in TG transester-
catalysts in transesterification reactions of dierent Brazilian
ification reactions under homogeneous catalysis conditions
vegetal oils, which are potentially useful as raw material for
is yet few explored in the literature comparatively to the
biodiesel production. The main results are summarized in
use of heterogeneous metal catalysts. Recently, some catalysts
Table 8.
based on tin(II) salts (i.e., tin(II) acetate, tin(II) chloride,
In that work, those authors [11] proposed a mechanism
tin(II) 2-ethylhexanoate, and tin(II) stearate) were applied
for the transesterification reaction catalyzed by pyrone-metal
in transesterification and esterification reactions of acidic
complexes as described in Figure 9. In Figure 10, was used
vegetable oils [29]. When catalysts were tested in the simul-
a monoester as model molecule, whereas the triglyceride,
taneous trans- and esterification of acidic oil, the formation
which is the real substrate in the transterification reactions.
of water deactivated the catalyst tin(II) 2-ethylhexanoate.
As can be seen in Figure 10, it was proposed that in
Best results were obtained with tin(II) acetate (methyl ester
the coordination sphere of the metal cation the bidentade
content, 96.6 wt.% at 150 C and 3 h). A comparison between
pyrone ligand is replaced by CH3 OH; after elimination of the
these results and those achieved by tin(II)-pyrone complex
protonated ligand, the vacancy generated is then occupied
reveals that the tin salts catalysts required higher work
by the fatty monoester which is coordinated via carbonyl
temperatures than tin(II)-pyrone catalysts.
group. Thus, after the nucleophilic attack of methyl alcohol
on the ester coordinated to metal complex, a four-center
cyclic intermediate is formed, which is then decomposed 2.2.3. Catalysts Based on Organometallic Complexes of Tin
into R2 OH alcohol and R1 COOCH3 fatty ester methyl. From Applied on TG Transesterification Reactions. Whereas most
this point the catalyst once more has one free vacancy for of the industrially inorganic tin(II) and tin(IV) compounds
the coordination of another molecule of fatty ester. Despite can be obtained directly from tin metal, the production of
the successful use of these catalysts, their application in the tin organometallics always involves conversion of tin(IV)
8 ISRN Renewable Energy

Table 8: Alcoholysis of soybean oil and methanolysis of dierent Brazilian vegetable oils catalyzed by sulfuric acid or Sn(II)-pyrone complexa .

H2 SO4 catalyst Sn(II)-pyrone catalyst

Entry Alcohol
Ester yield after 1 hour reaction (%)b
1 Methyl 1.4 37.1
2 Ethyl 1.0 8.3
3 Propyl 4.2
Entry Oil Ester yield after 1 hour reaction (%)b
4 Andiroba 3.8 23
5 Babacu 12.5 35.6
6 Palm tree 8.5 16.2
Reaction conditions: alcohol : vegetable oil : catalyst molar ratio (400 : 100 : 1), 60 C temperature, and magnetically stirred.

H3 C O O
H 3C O O O
O R1 -COO-R2 M 3
R2 O C R1
R2 O C R1

Figure 10: Proposed mechanism for the transesterification with methyl alcohol catalyzed by pyrone-metal complexes [11].

chloride to the corresponding tetraorganotin, followed by Those authors investigated the eect of transesterification
reactions to produce the required derivative. Nevertheless, reaction temperature on FAMEs yield and found that the
despite that the synthesis of the catalysts has importance, DBTDL organotin catalyst, which is most soluble catalyst was
there are two others crucial points that determine for organ- the most eective in any temperature assessed (Figure 11).
otin catalysts, eciency in the transesterification reactions: Actually, Sn(IV) catalysts solubility can be increased
its solubility and the temperature of work. on increasing the reaction temperature; however, because
It should be noted that although the solubility is directly the methyl alcohol is frequently used in transesterification
aected by temperature, both can aect in dierent ways reactions, another important aspect arises: the reactions
the eciency of organotin(IV) catalysts in transesterification performed at high temperatures (up to boiling point 60 C
reactions of vegetable oil. Literature report that at higher methyl alcohol) requires a reactor that works under high
temperatures tin catalysts can be eectively activated and intern pressure. The amount of methyl alcohol present in
their solubility in the reaction medium can be increased the liquid phase will depend on the reactor pressure. Conse-
[30, 31]. Moreover, organotin(IV) compounds like as di-n- quently, the reactor type can also aect the transesterification
butyl-oxo-stannane (DBTO) and butyl stannoic acid (BTA) reaction yields catalyzed by organotin(IV) compounds.
are insoluble at room temperatures in several solvents; Recently, Meneghetti and coworkers investigated the
however, on increasing the temperature their structure can eciency of organotin catalysts using two dierent reactors:
be destroyed and more active species are formed [31]. an open glass reactor (OG) and a close steel reactor (CS) [13].
Thus, the activity of the organotin catalysts should be The first reactor type open glass (OG), was equipped with
evaluated considering both their solubility in the reaction a bath with temperature control, reflux condenser, and mag-
conditions as well as work temperature. Meneghetti and netic stirrer, which is able only to operate at solvent reflux
coworkers [12] described some solubility data of typical temperature and the second, a reactor type closed steel
Sn(IV) organocatalysts, which are displayed in Table 9. (CS), a batch stainless steel reactor coupled to a manometer,
The experimental data described by those authors indi- temperature probe, and magnetic stirrer. Those authors have
cated that expectedly, the DBTDL catalyst that, has higher investigated the catalytic activity of Sn(IV) compounds (i.e.,
alkyl group than others organotin(IV) catalysts was com- dibutyl tin diacetate (DBTDA), butyl stannoic acid (BTA),
pletely soluble in oil or FAMEs. This observation certainly di-n-butyl-oxo-stannane (DBTO), and dibutyl tin dilaurate
justifies the high catalytic activity of DBTDL observed in (DBTDL)), in the soybean oil transesterification reactions
the several transesterification reactions. Ferreira and co- with dierent alcohols [13].
workers [12] testing a class of commercial organometallic Initially, they investigated the eect of type of reactor,
compounds of tin as catalysts in transesterification reactions performing the reactions with catalysts DBTO and DBTDA
of soybean oil with methyl alcohol are shown in Table 10. in two reactors studied (i.e., OG and CS) (Figure 12).
Those authors concluded that the catalytic activity was The results obtained indicated that, regardless of the
related to the enhancement of the solubility of the Sn(IV) Sn(IV) catalyst employed, the reactions performed in CS
catalyst into the reaction solution. Indeed, the solubility of reactor achieved higher conversion [13]. This fact can be
the catalyst can be molded by varying either size and/or num- attributed to higher amount of CH3 OH present in liquid
ber of the alkyl chains in the structure of the catalysts [12]. phase, due to higher internal pressure (autogenic pressure).
ISRN Renewable Energy 9

Table 9: Degree of solubility of typical organotin(IV) catalysts applied in the transesterification reactions [12].

Solubility (gmL1 ) at 40 C Solubility (gmL1 ) at 100 C

Organotin catalyst
Methyl alcohol Soybean oil FAMEs Methyl alcohol Soybean oil FAMEs
dibutyltin dilaurate (DBTDL) 0.02 0.02 Soluble Soluble Soluble
di-n-butyl-oxo-stannane (DBTO) Insoluble Insoluble <0.01 0.10 0.15
Butylstannoic acid (BTA) Insoluble Insoluble <0.01 0.03 0.04
Detection limit was 0.01 gmL1 .

Table 10: Chemical composition and commercial nomenclature of tin(IV) catalysts [12].

Catalyst Chemical formula Commercial denomination

(C4 H9 )SnO(OH)
FASCAT 4100 Butylstannoic acid
(C4 H9 )2 SnO
FASCAT 4201 Di-n-butyloxo-stannane
Modified (C4 H9 )2 SnO
FASCAT 4350 Modified di-n-butyl-oxo-stannane
Modified DBTO
(C4 H9 )2 Sn(C12 H23 O2 )2 ;
FASCAT 118 Dibutyltindilaurate
Reaction conditions: molar ratio CH3 OH : oil : catalyst = 400 : 100 : 1, 80 C, 1000 rpm, and open glass.


40 50
FAMEs yields (%)

FAMEs (%)


20 20
0 1 2 3 4
60 70 80 90 100 110 120
Time (h)
Temperature ( C)
DBTO (OG reactor) DBTO (CS reactor)
DBTDA (OG reactor) DBTDA (CS reactor)
Figure 12: FAMEs yields obtained from transesterification of
Figure 11: FAMEs yields obtained from methanolysis of soybean oil
soybean oil with methyl alcohol in the presence of Sn(IV) catalysts
in the presence of commercial Sn(IV) catalysts [12]. Reaction con-
performed in two dierent reactora (OG and OS) [13]. (Reaction
ditions: molar proportions of MeOH : oil : catalyst = 400 : 100 : 1,
conditions: molar ratio CH3 OH : oil : catalyst = 400 : 100 : 1, 80 C,
magnetic stirring (1000 rpm).
1000 rpm, open glass).

If a reaction is performed at conditions whereby one of the in solution of reaction; in the CS reactor, temperatures
reagents is in reflux, for example, in fast equilibrium between higher than methyl alcohol boiling point are reached in
the gas and liquid phases, its concentration, in the phase solution and consequently an eective activation of catalysts
where the reaction actually occurs, is lower than expected, is achieved and at least, the increase on temperature enhance
because part of the respective reagent is in the gas phase [13]. the solubility of organotin(IV) catalysts [13].
For this reason, the reactions performed in the OG reactor Figure 13 displays the results described by de Mendonca
achieved lower conversions than those reactions performed and coworkers [13] and confirms that when the tin catalyst
in the CS reactor. Thus, the high eciency of tin(IV) has group alkyl less polar its activity is enhanced. For
catalysts in reactions done on the reactors CS to four distinct this reason, DBTDA and DBTDL were the most eective
features: the higher concentration of the methyl alcohol catalysts in transesterification of soybean oil. The eect of
10 ISRN Renewable Energy

70 Table 11: Yields of FAMEs obtained from transesterification of

soybean oil with methyl alcohol in the presence of Sn(IV) catalysts
60 performed in a CS reactora [13].

50 FAMEs yields (%)

Temperature ( C)
FAMEs yields (%)


40 80 75 64
120 77 76 85 60
150 79 80 74 74
20 Reaction conditions: molar proportions of MeOH : oil : catalyst =
400 : 100 : 1, magnetic stirring (1000 rpm), and 4 hours reaction.
Table 12: Yields of fatty esters obtained from DBTDL-catalyzed
0 soybean oil transesterification with dierent alcohols performed in
0 2 4 6 8 10
CS or OG reactorsa [13].
Time (h)
Alcohol Temperature ( C) Reactor Yield
Methyl 64 CS 38
Figure 13: FAMEs yields obtained from transesterification of
150 CS 98
soybean oil with methyl alcohol in the presence of Sn(IV) catalysts
[13]. (Reaction conditions: molar ratio CH3 OH : oil : catalyst = 78 CS 30
400 : 100 : 1, 80 C, 1000 rpm, open glass reactor). Ethyl
150 CS 82
iso-propyl 150 CS 57
108 OG 26
the temperature was also assessed and the main results are
iso-butil 108 CS 67
summarized in Table 11.
Noticeably, the BTA catalyst was much more sensible to 150 CS 82
increase on temperature than others catalysts; the FAMEs Reaction conditions: molar proportions of alcohol : oil : catalyst =
yields in presence of this catalyst jumped of 10 for 73% 400 : 100 : 1, magnetic stirring (1000 rpm).
when the temperature was increased of 80 for 150 C. In
reactions performed at 150 C, after 4 hours reaction all Table 13: Yields of FAMEs obtained from brain rice oil transester-
Sn(IV) catalysts reached conversions between 74 and 80%. ification with methyl alcohol with dierent catalysts performed in
As expected, regardless the type of alcohol substrate used, CS reactorsa [14].
the reactions performed in CS reactor reached higher yield Run Catalyst Time Yield
than those performed in OG reactor. In relation to the eect
1 1 5.6
of the type of alcohol, those authors (Table 12) observed that DBTL
2 5 65.8
an increase in the carbon chain length favored the reaction
yield reaction. This eect can be attributed to the increase 3 1 17.5
Sn(C8 H15 O2 )2
of solubility of DBTDL catalyst in less polar alcohols. The 4 4 1.21
hindrance on alcohol hydroxyl also aect the reactions yield, 5 1 9.5
however, in the case of iso-butil alcohol, this negative eect 6 5 29.9
has been minimized by the increase of catalyst solubility. 7 1 0.9
Consequently, it was more reactive than iso-propyl alcohol. 8 5 0.6
Finally, as general tendency, higher yields were achieved at 9 1 8.3
higher temperatures. H2 SO4
10 5 36.2
Einloft and coworkers [14] investigated the transes- a
Reaction conditions: molar proportions of methyl alcohol : brain rice
terification of rice bran oil with methyl alcohol in the oil : catalyst = 40 : 100 : 1, magnetic stirring (1000 rpm), and reflux tempera-
presence of organotin catalysts allowing tin 2-ethylhexanoate ture.
(Sn(C6 H15 O2 )2 ), dibutyl tin oxide ((C4 H9 )2 SnO), dibutyl
tin dilaurate ((C4 H9 )2 Sn (C12 H23 O2 )2 ). These two latter
catalysts are known commercially as DBTO and DBTDL, noting that although it is not shown herein, those authors
respectively, (Table 13). Sulfuric acid and tin chloride dihy- found that kinetics behaviors of Brnsted acid catalysts
drate were selected for comparison. are distinct when compared to organotin compounds. On
They verified that in the reaction conditions described one hand, the Brnsted acid-catalyzed transesterification
in Table 13, the DBTDL catalyst was the more eective in reactions starts at a slow rate, continues at a faster rate,
the biodiesel synthesis. The final yield was 65.8% methyl and then slows again as the reaction nears completion. On
esters in a reaction time of 5 h. In the same conditions, a the other hand, the tin catalysts have dierent activities
Brnsted acid catalyst presented a yield of 36.2%. It is worth in the transesterification reactions. The ligand eect on
ISRN Renewable Energy 11

Table 14: Tin(IV) organometallics catalysts applied on TG transesterification reactions.

Dibutyl tin diacetate Dibutyl tin dilaurate Dibutyl stannoic acid di-n-butyl-oxo-stannane

Sn O
O Sn

(C4 H9 )2 Sn(C2 H3 O2 )2 (C4 H9 )2 Sn(C12 H23 O2 )2 (C4 H9 )SnO(OH) (C4 H9 )2 SnO


Table 15: Yields of FAMEs obtained from castor oil transesterification and soybean oil with methyl alcohol performed in CS and OG reactors
in presence of Sn(IV) catalysts at dierent temperaturesa [15].

Sn(IV) catalysts
Reactor temperature ( C) Time (h) DBTDA DBTDL DBTO BTA
Soybean oil Castor oil Soybean oil Castor oil Soybean oil Castor oil Soybean oil Castor oil
2 13 <5 11 <5 <5 6 <5 <5
4 23 <5 20 <5 7 <5 <5 <5
2 63 <5 48 7 48 12 10 <5
CS; 80
4 75 <5 62 8 64 16 9 <5
2 73 47 77 23 83 26 76 14
4 77 64 76 36 85 43 60 35
2 65 46 98 52 95 50 73 53
CS; 150
4 79 56 80 57 75 50 74 61
Reaction conditions: molar proportions of methyl alcohol : oil : catalyst = 400 : 100 : 1, magnetic stirring (1000 rpm).

the behavior of tin catalysts during the transesterification This lower activity of the catalysts on transesterification
reactions may be justifies their higher or lower activity com- of castor oil is not due to mass transfer problems, but rather
paratively to sulfuric acid. This behavior can be attributed to the unique chemical composition of this oil, which has
to the chemical structure which plays an important role in as major constituent, the ester of the ricinoleic acid, that
transesterification reaction, modifying both the solubility in contains an undesirable hydroxyl group in their structure.
the reaction medium and/or the Lewis acidity of the metallic This observation indicates the influence of the chemical
center [15, 32, 33]. It deserves highlights that although the composition of the triglycerides on the catalytic activity of
yields obtained in DBTL-catalyzed are not as high as 80 Lewis acid sites [15].
90%, it is almost two-times higher than those obtained in
H2 SO4 -catalyzed reactions. Moreover, all transesterification 2.3. General Remarks. In summary, the three main types of
reactions were performed at mild conditions (methyl alcohol compounds based on tin (i.e., tin(II) chloride, tin(II)-pyrone
reflux temperature). complexes, and tin(IV) organometallic complexes) are cata-
Recently, Meneghetti and coworkers studied the eect of lysts potentially attractive for biodiesel production. However,
type oil in the transesterification reactions in presence of they have specific characteristics that make the their use more
tin(IV) organometallics catalysts: soybean oil and castor oil eective in the esterification reactions (i.e., tin(II) chloride)
were the oils assessed [15]. The organotin catalysts selected or in the transesterification reactions (i.e., tin(II) pyrone
by those authors were (C4 H9 )2 Sn(C12 H23 O2 )2 (DBTDL), complexes and tin(IV) organometallic complexes). Although
(C4 H9 )2 Sn(C2 H3 O2 )2 (DBTDA), (C4 H9 )2 SnO (DBTO), and not active in TG transesterification processes, tin(II) chloride
(C4 H9 )SnO(OH) (BTA) (Table 14), which were applied in catalyst is so much suitable for use in FFA esterification
dierent temperature (Table 13). reactions due to its commercial availability, high water
Meneghetti and co workers confirmed that the reactions tolerance, low cost, high activity, and possibility of reuse even
performed in CS reactor were more ecient than those in homogenous catalysis conditions. On the other hand, both
performed in OG reactor (Table 15) [15]. Moreover, the most tin(II)-pyrone and tin(IV) organometallic complexes proved
soluble catalysts were again the most actives. However, an to be ecient in vegetable oil transesterification reactions.
interesting eect was found. It was found that regardless the Nevertheless, they have key features which dierentiate them
temperature of reaction and the Sn(IV) catalyst employed, from each other. Organotin(IV) catalysts have their solu-
the transesterification with methyl alcohol of the castor oil bility and performance drastically aected by the reaction
leads to lower yields than those observed when soybean oil conditions (i.e., type of reactor (CS or OG) and also the
was the triglyceride source [15]. reaction temperature). In general, among the organotin(IV)
12 ISRN Renewable Energy

catalysts studied (i.e., (C4 H9 )2 Sn(C12 H23 O2 )2 (DBTDL), the heterogeneous catalysts based on tin will be potentially
(C4 H9 )2 Sn(C2 H3 O2 )2 (DBTDA), (C4 H9 )2 SnO (DBTO), and performed via anchoring tin complexes on the solid matrixes
(C4 H9 )SnO(OH) (BTA)), DBTDA and DBTDL were the with high surface area, as well as via traditional processes
most eective. However, both DBTDA and DBTDL were such as tin salts impregnation on metal oxides or sol-gel
noticeable less active than tin(IV)-pyrone complex in the methods.
soybean oil transesterification same reaction conditions With the data shown in this paper, we hope that we have
(80 C temperature, 4 hours reaction). When in the Sn(II)- demonstrated that catalysts based on tin have great potential
pyrone-catalyzed reactions, the maximum yields (up to 90%) to replace the systems currently employed in the biodiesel
was obtained after 6 hours reaction; conversely, organ- industry, and that this replacement oers advantages that
otin(IV) catalysts reached FAMEs yield maximum equal to provide a considerable increase in the prospects for sustain
64%. friendly environmentally production processes.
Nevertheless, novel results were recently published in
whichthree Sn(IV) complexes, named butyl stannoic acid
(BTA), di-n-butyl-oxo-stannane (DBTO), and dibutyltin Acknowledgments
dilaurate (DBTDL), were tested as catalysts in simultane- This work has been financially supported by the FAPEMIG,
ous esterification/transesterification reactions performed at CAPES, and CNPq.
160 C temperature using methyl alcohol. In these condi-
tions, it was verified that BTA was best catalyst [34].
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